JP2003249170A - Display panel and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a display panel with a structure where fluorescent particles are not easily deteriorated despite collision of electrons. <P>SOLUTION: The manufacturing method for the display panel comprises the steps of; dipping a substrate 20 on which a fluorescent layer 22 is formed into liquid filled in a process tank so that the fluorescent layer 22 faces a liquid surface side (a); forming an intermediate film 23 on the liquid surface (b); leaving the intermediate film 23 on the fluorescent body 22 by lowering the liquid surface by ejecting the liquid from the process tank (c); drying the intermediate film 23 (d); forming a reflecting film 24 on the intermediate film 23 (e); and baking the intermediate film 23 (f). The glass transition temperature of resin forming the intermediate film is from 15°C to 30°C. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display panel and a method for manufacturing the same, and more particularly, to a phosphor layer, and the phosphor layer is formed when electrons emitted from an electron beam source collide with the phosphor layer. The present invention relates to a display panel for emitting light to obtain a desired image and a manufacturing method thereof.

[0002]

2. Description of the Related Art In the field of display devices used in television receivers and information terminal equipment, conventional cathode ray tubes (C) have been used.
The shift from RT) to a flat-panel (flat-panel) display device that can meet the demands for thinner, lighter, larger screen, and higher definition is under study. Liquid crystal display (LCD), electroluminescent display (ELD), plasma display (PD
P) and a cold cathode field emission display (FED: field emission display). Among them, the liquid crystal display device is widely used as a display device for information terminal equipment, but it is still problematic to increase the brightness and size for application to a stationary television receiver. . On the other hand, the cold cathode field emission device is a cold cathode field emission device (hereinafter referred to as a field emission device) capable of emitting electrons from a solid body into a vacuum based on a quantum tunnel effect without relying on thermal excitation. It may be called an element), and is attracting attention because of its high brightness and low power consumption.

FIG. 3 is a schematic partial end view of a cold cathode field emission display device (hereinafter also referred to as a display device) using a field emission device, and a schematic partial view of a cathode panel CP. A perspective view is shown in FIG. The illustrated field emission device is a so-called Spindt type field emission device having a conical electron emission portion 15. This field emission device includes a cathode electrode 11 formed on a support 10, an insulating layer 12 formed on the support 10 and the cathode electrode 11, a gate electrode 13 formed on the insulating layer 12, and a gate. A first opening 14A provided in the electrode 13, a second opening 14B provided in the insulating layer 12 and communicating with the first opening 14A, and a second opening 1
It is composed of a conical electron emitting portion 15 formed on the cathode electrode 11 located at the bottom of 4B. In general,
The cathode electrode 11 and the gate electrode 13 are formed in stripes in the directions in which the projection images of these two electrodes are orthogonal to each other, and a region corresponding to a portion where the projection images of these two electrodes overlap (one pixel A plurality of field emission devices are usually provided in this region (hereinafter referred to as an overlapping region). Further, such overlapping areas are usually arranged in a two-dimensional matrix in the effective area of the cathode panel CP (area that functions as an actual display screen).

On the other hand, the anode panel AP is a substrate 20.
And a phosphor layer 22 formed on the substrate 20 and having a predetermined pattern, and an anode electrode 24 formed thereon, which also functions as a reflective film. 1 pixel is
Cathode electrode 11 and gate electrode 13 on the cathode panel side
And a phosphor layer 22 on the anode panel side facing the group of field emission devices. Such pixels are arrayed in the order of, for example, hundreds of thousands to several millions in an effective region that is a region that functions as an actual display portion. A partition wall 21 is formed on the substrate 20 between the phosphor layers 22. FIG. 5 schematically shows an example of the arrangement of the partition walls 21, the spacers 25, and the phosphor layer 22.

Anode panel AP and cathode panel CP
The display device can be manufactured by arranging and so that the field emission element and the phosphor layer 22 face each other and joining them at the peripheral portion with the frame 30 interposed therebetween. A through hole (not shown) for evacuation is provided in the ineffective area that surrounds the effective area and in which a peripheral circuit for selecting pixels is formed, and this through hole is completely sealed after evacuation. The tip tube (not shown) is connected. That is, the space surrounded by the anode panel AP, the cathode panel CP, and the frame body 30 is vacuum. In addition, pressure is applied to the anode panel AP and the cathode panel CP by the atmosphere. The so-called spacer 25 having a height of, for example, about 1 mm is provided between the anode panel AP and the cathode panel CP so that the display device is not damaged by this pressure.
(See FIG. 5) are arranged. In addition, in FIG.
Illustration of the spacer is omitted.

A relative negative voltage is applied to the cathode electrode 11 from the cathode electrode control circuit 31, and the gate electrode 13
, A relative positive voltage is applied from the gate electrode control circuit 32, and a higher positive voltage than the gate electrode 13 is applied from the anode electrode control circuit 33 to the anode electrode 24. When displaying on such a display device, for example,
A scanning signal is input to the cathode electrode 11 from the cathode electrode control circuit 31, and a gate electrode control circuit 3 is input to the gate electrode 13.
Input video signal from 2. An electric field generated when a voltage is applied between the cathode electrode 11 and the gate electrode 13 causes electrons to be emitted from the electron emitting portion 15 based on the quantum tunnel effect, and the electrons are attracted to the anode electrode 24 to cause the anode electrode 24 to move. It passes through and collides with the phosphor layer 22. As a result, the phosphor layer 22 is excited and emits light, and a desired image can be obtained. That is, the operation and brightness of this display device are basically determined by the voltage applied to the gate electrode 13 and the electron emitting portion 15 through the cathode electrode 11.
It is controlled by the voltage applied to.

The anode electrode 24 has a function as a reflecting film for reflecting the light emitted from the phosphor layer 22, and also the phosphor layer 2
It has a function as a reflection film for reflecting the electrons recoiled from 2 or the emitted secondary electrons, and a function for preventing the phosphor layer 22 from being charged. Further, the partition wall 21 is formed of the phosphor layer 2
2 has a function of preventing electrons recoiled from 2 or secondary electrons emitted from the phosphor layer 22 from entering another phosphor layer 22 and causing so-called optical crosstalk (color turbidity). .

Hereinafter, with reference to FIGS. 1A to 1F and FIG. 19, an anode panel AP in a conventional display device will be described.
The outline of the manufacturing method will be described.

[Step-10] First, the partition wall 21 is formed on the substrate 20 made of a glass substrate (see FIG. 1A).

[Step-20] Next, in order to form a red light emitting phosphor layer, for example, polyvinyl alcohol (PV
A) red light emitting phosphor particles are dispersed in resin and water, and further,
After applying the red light emitting phosphor slurry to which ammonium dichromate has been added to the entire surface, the red light emitting phosphor slurry is dried, exposed and developed to give a predetermined partition wall 2.
The red light emitting phosphor layer 22R is formed between the two (see FIG. 1B). By performing such an operation similarly for the green light emitting phosphor slurry and the blue light emitting phosphor slurry, finally, the red light emitting phosphor layer 22R and the green light emitting phosphor layer 22G are provided between the predetermined partition walls 21. To form a blue light emitting phosphor layer 22B ((C) of FIG. 1 and FIG.
(See the schematic partial layout drawing).

[Step-30] After that, each phosphor layer 22 is formed.
An intermediate film 23 mainly composed of lacquer mainly composed of nitrocellulose is formed on R, 22G and 22B (these may be collectively referred to as a phosphor layer 22) ((D in FIG. 1). )reference). Specifically, the substrate 20 on which the phosphor layer 22 is formed is submerged in the water tank, a lacquer film is formed on the water surface, and then the water in the water tank is drained to remove the intermediate film 23 made of lacquer from the phosphor layer 22. It can be formed from above to above the partition wall 21.

[Step-40] After that, the anode electrode 24 made of aluminum is formed on the entire surface by a vacuum deposition method (see FIG. 1E). Finally, the intermediate film 23 is baked by performing a heat treatment at about 400 ° C., whereby a structure as shown in FIG. 1F can be obtained. 19 is an enlarged schematic view of the phosphor layer 22, the anode electrode 24, and the partition wall 21.

The anode electrode 24 on the phosphor layer 22 is
It is almost flat. On the other hand, since the phosphor layer 22 is composed of many phosphor particles, the top surface of the phosphor layer 22 is uneven. Therefore, the anode electrode 24 is in a kind of point contact state with the phosphor particles forming the phosphor layer 22, or in a state where the contact area is small as shown in the schematic view of FIG. 19 or FIG.

[0014]

By the way, when the anode electrode 24 and the phosphor particles are in the contact state shown in FIG. 19 or FIG. 20, the phosphor particles are deteriorated by the collision of electrons with the phosphor layer 22. It has turned out to be noticeable. When further observing such deteriorated phosphor particles,
The portion of the phosphor particles that are not in contact with the anode electrode 24 is more significantly deteriorated than the portion of the phosphor particles that is in contact with the anode electrode 24. It is presumed that such local deterioration of the phosphor particles is caused by local charging of the phosphor particles due to collision of electrons with the phosphor particles, temperature rise of the phosphor particles, evaporation of the phosphor particles, and the like. . Such deterioration of the phosphor particles brings about a shortened life of the display device and is therefore an important problem that must be avoided.

Accordingly, it is an object of the present invention to provide a display panel having a structure in which phosphor particles are not easily deteriorated by collision of electrons, and a method of manufacturing such a display panel.

[0016]

A method for manufacturing a display panel according to a first aspect of the present invention for achieving the above object comprises a substrate (A) and a phosphor particle (B) on a substrate. At least a phosphor layer formed on the phosphor layer, and (C) a reflective film formed of a metal thin film formed on the phosphor layer.
A method of manufacturing a display panel for emitting a desired image, which is emitted from an electron beam source, emits a phosphor layer by colliding electrons passing through a reflective film with the phosphor layer,
(A) a step of immersing the substrate on which the phosphor layer is formed in a liquid filled in a processing tank so that the phosphor layer faces the liquid surface side; and (b) an intermediate film on the liquid surface. Forming process,
(C) a step of leaving the intermediate film on the phosphor layer by discharging the liquid from the treatment tank to lower the liquid level; (d) a step of drying the intermediate film; and (e) reflection on the intermediate film. And a step of (f) baking the intermediate film,
The glass transition temperature of the resin constituting the intermediate film is 15 ° C to 30 ° C.

In the method for manufacturing a display panel according to the first aspect of the present invention, in the step (b), the organic film in which the resin forming the intermediate film is dissolved is dropped onto the liquid surface to form the intermediate film. It is preferably formed. It is also preferable to use water as the liquid.

Second aspect of the present invention for achieving the above object
The manufacturing method of the display panel according to the aspect of (A) is a substrate,
Emitting from an electron beam source, which comprises at least (B) a phosphor layer formed of phosphor particles on a substrate, and (C) a reflective film formed of a metal thin film formed on the phosphor layer. The phosphor layer emits light when electrons passing through the reflective film collide with the phosphor layer, and a method for manufacturing a display panel for obtaining a desired image, comprising: (a) forming the phosphor layer Water is sprinkled on the surface of the formed substrate to form a thin film of water on the entire surface, (b) a step of forming an intermediate film on the thin film of water, and (c) evaporation of the thin film of water. The step of leaving the intermediate film on the phosphor layer, (d) the step of forming a reflective film on the intermediate film, and (e) the step of baking the intermediate film are performed. It is characterized in that the glass transition temperature is 15 ° C to 30 ° C.

In the method for manufacturing a display panel according to the second aspect of the present invention, in the step (b), the organic solvent in which the resin forming the intermediate film is dissolved is sprayed onto the thin film made of water. It is preferable to form an intermediate film.

In the method of manufacturing a display panel according to the first or second aspect of the present invention (hereinafter, these may be collectively referred to as the method of manufacturing a display panel of the present invention) The glass transition temperature (glass transition point) of the resin that constitutes the intermediate film is Rheometric Scientific, In
c. It is a value measured using an RSA III viscoelasticity analyzer (for solid), and mechanical loss (mechanical loss) tan δ (also called logarithmic damping rate λ) is obtained based on the measurement of dynamic viscoelasticity characteristics. The maximum value of the mechanical loss tan δ curve with temperature as a parameter is the glass transition temperature T _g ,
It corresponds to the second-order transition temperature of the substance.

In the display panel manufacturing method of the present invention, it is desirable that the resin forming the intermediate film is an acrylic resin. Examples of the acrylic resin include methyl methacrylic resin, methacrylic copolymer resin, ethyl methacrylic resin, and butyl methacrylic resin. Toluene, ethyl alcohol, mineral spirits, isoamyl acetate, butanol and xylene can be exemplified as the organic solvent that dissolves the resin forming the intermediate film.

The display panel of the present invention for achieving the above object comprises (A) substrate and (B) phosphor particles.
At least a phosphor layer formed on the substrate and (C) a reflective film made of a metal thin film formed on the phosphor layer are provided, and electrons emitted from the electron beam source and passing through the reflective film are The phosphor layer emits light by colliding with the phosphor layer,
A display panel for obtaining a desired image, wherein the area of the projected image of the phosphor particles in contact with the reflective film in the substrate normal direction is S ₀ , and the contact area of the phosphor particles with the reflective film is S ₁ Then, 1.9S ₀ ≦ S ₁ , preferably 2.0S ₀ ≦ S ₁
Is satisfied.

In the display panel of the present invention, observation is performed from the reflective film side using a scanning electron microscope (SEM). At this time, by appropriately selecting the high voltage of the scanning electron microscope, the portion of the phosphor particles in contact with the reflective film can be clearly identified. By processing the image data, S ₁ / S ₀ can be obtained.

In the display panel of the present invention, the phosphor layer is composed of a plurality of phosphor particles, and the surface (top surface) of the phosphor layer is uneven. Therefore, the reflective film is not in contact with all the phosphor particles forming the surface (top surface) of the phosphor layer. The definition of the areas S ₀ and S ₁ in the display panel of the present invention relates to the phosphor particles in contact with the reflective film. The definition of the areas S ₀ and S ₁ in the display panel of the present invention does not apply to the phosphor particles that are not in contact with the reflective film.

In the display panel of the present invention or the method for manufacturing the same, the reflective film is preferably made of aluminum (Al) or chromium (Cr). For example, the reflective film may be formed by vapor deposition or sputtering. it can. The reflective film preferably has a thickness that allows most of the electrons accelerated in the phosphor layer that are accelerated at high speed to pass through. In this case, specifically, the reflective film has a thickness of 3 × 10 ^{−. 8} m
(30 nm) to 1.5 × 10 ⁻⁷ m (150 nm), preferably 5 × 10 ⁻⁸ m (50 nm) to 1 × 10 ⁻⁷ m
(100 nm) is desirable. By "fastly accelerated electrons" is meant electrons that have been accelerated by a potential difference of 3 kilovolts to 10 kilovolts, preferably 6 kilovolts to 10 kilovolts. Further, "pass most of the electrons" means that 60%, preferably 80% or more of the electrons incident on the reflective film pass through the reflective film. Alternatively, the reflection film reflects electrons recoiled from the phosphor layer or secondary electrons emitted from the phosphor layer toward the phosphor layer, or absorbs these electrons in the reflection film. The thickness is preferably such that
In this case, the proportion of electrons recoiled from the phosphor layer or secondary electrons emitted from the phosphor layer passing through the reflective film is preferably 60% or less, more preferably 30% or less.

In the display panel of the present invention or the manufacturing method thereof, the reflective film also functions as an anode electrode,
The display panel may be in the form of an anode panel of a cold cathode field emission display. Alternatively, the anode electrode may be formed between the phosphor layer and the substrate, and the display panel may form an anode panel of a cold cathode field emission display. In these cases, the electron beam source is composed of a cold cathode field emission device provided in a cathode panel constituting a cold cathode field emission display device.

The substrate constituting the display panel or the anode panel and the support constituting the cathode panel are required to have at least a surface made of an insulating member, such as a non-alkali glass substrate, a low alkali glass substrate, and a quartz glass substrate. Such as various glass substrates, various glass substrates having an insulating film formed on the surface, a quartz substrate, a quartz substrate having an insulating film formed on the surface, and a semiconductor substrate having an insulating film formed on the surface. From the viewpoint of reducing the manufacturing cost, it is preferable to use a glass substrate or a glass substrate having an insulating film formed on its surface.

The phosphor layer may be formed in stripes or dots corresponding to the pixels. For the phosphor layer, a luminescent crystal particle composition prepared from luminescent crystal particles (for example, phosphor particles having a particle size of about 5 to 10 nm) is used. For example, a red photosensitive luminescent crystal particle composition is used. (Red phosphor slurry) is applied to the entire surface, exposed and developed to form a red light emitting phosphor layer, and then a green photosensitive luminescent crystal particle composition (green phosphor slurry) is applied to the entire surface. Then, it is exposed to light and developed to form a green light emitting phosphor layer, and further, a blue photosensitive light emitting crystal particle composition (blue phosphor slurry) is applied on the entire surface, exposed to light and developed to emit blue light. It can be formed by a method of forming a phosphor layer.

The phosphor material forming the luminescent crystal particles can be appropriately selected and used from conventionally known phosphor materials. In the case of color display, the color purity is NTSC
It is preferable to combine phosphor materials that are close to the three primary colors defined in (3), have a white balance when the three primary colors are mixed, and have a short afterglow time and a substantially equal afterglow time of the three primary colors. As a phosphor material forming the red light emitting phosphor layer,
(Y ₂ O ₃ : Eu), (Y ₂ O ₂ S: Eu), (Y ₃ Al ₅ O
₁₂ : Eu), (YBO ₃ : Eu), (YVO ₄ : Eu),
(Y ₂ SiO ₅ : Eu), (Y _0.96 P _0.60 V _0.40 O ₄ : E
u _0.04 ), [(Y, Gd) BO ₃ : Eu], (GdB
O ₃ : Eu), (ScBO ₃ : Eu), (3.5 MgO.
0.5MgF ₂ · GeO ₂ : Mn), (Zn ₃ (P
O ₄ ) ₂ : Mn), (LuBO ₃ : Eu), (SnO ₂ : E)
u) can be illustrated. As the phosphor material forming the green light emitting phosphor layer, (ZnSiO ₂ : Mn), (B
aAl ₁₂ O ₁₉ : Mn), (BaMg ₂ Al ₁₆ O ₂₇ : M
n), (MgGa ₂ O ₄ : Mn), (YBO ₃ : Tb),
(LuBO ₃ : Tb), (Sr ₄ Si ₃ O ₈ Cl ₄ : E
u), (ZnS: Cu, Al), (ZnS: Cu, A)
_{u, Al), (ZnBaO 4} : Mn), (GbBO 3: T
b), (Sr ₆ SiO ₃ Cl ₃ : Eu), (BaMgAl
₁₄ O ₂₃ : Mn), (ScBO ₃ : Tb), (Zn ₂ SiO)
₄ : Mn), (ZnO: Zn), (Gd ₂ O ₂ S: T
b) and (ZnGa ₂ O ₄ : Mn) can be exemplified. As a phosphor material constituting the blue light emitting phosphor layer,
(Y ₂ SiO ₅ : Ce), (CaWO ₄ : Pb), CaW
O ₄ , YP _0.85 V _0.15 O ₄ , (BaMgAl ₁₄ O ₂₃ : E
u), (Sr ₂ P ₂ O ₇ : Eu), (Sr ₂ P ₂ O ₇ : S
n), (ZnS: Ag, Al), (ZnS: Ag), Z
Examples thereof include nMgO and ZnGaO ₄ .

When the display panel of the present invention or the manufacturing method thereof is applied to the cold cathode field emission display or the manufacturing method thereof, the cold cathode field emission device constituting the cathode panel has any type of cold cathode field emission. The device may be an element, for example, a so-called Spindt-type cold cathode field emission device having a conical electron emission part, a so-called crown-type cold cathode field emission device having a crown-type electron emission part, and a flat electron emission part. A so-called flat type cold cathode field emission device, a flat type cold cathode field emission device in which electrons are emitted from the cathode electrode or a crater type cold cathode field emission device, and electrons are emitted from the edge part provided in the cathode electrode. Edge type cold cathode field emission devices can be mentioned. As the cold cathode field emission display, not only the so-called three-electrode type but also the so-called two-electrode type can be mentioned. Further, by the method for manufacturing a display panel of the present invention,
In addition, a fluorescent display tube can be manufactured.

In the method for manufacturing a display panel of the present invention, the glass transition temperature of the resin forming the intermediate film is 15 ° C.
By defining the temperature at 30 ° C to 30 ° C, it is possible to finally obtain a state in which the portion of the phosphor particles with which the electrons collide is in sufficient contact with the reflection film, and as a result, local deterioration of the phosphor particles occurs. It can be surely prevented. Further, in the display panel of the present invention, by defining the contact area of the phosphor particles with respect to the reflection film, it is possible to reliably prevent the local deterioration of the phosphor particles.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to the drawings on the basis of an embodiment of the invention (hereinafter, simply referred to as an embodiment).

(Embodiment 1) Embodiment 1 relates to a method for manufacturing a display panel according to the first aspect of the present invention, and more specifically, a cold cathode field emission display device (hereinafter, simply referred to as (Referred to as a display device) and a method of manufacturing a display panel corresponding to an anode panel.

The display device according to the first embodiment includes a cathode panel CP provided with a plurality of cold cathode field emission devices (referred to as field emission devices), a reflection film (anode electrode) 24 and a phosphor layer 22 (color). In the case of display, the red light emitting phosphor layer 22R, the green light emitting phosphor layer 22G, and the blue light emitting phosphor layer 2
The anode panel AP on which 2B) is formed is joined at their peripheral portions. The space sandwiched by the anode panel AP and the cathode panel CP is in a vacuum state.

In the display panel (anode panel AP) of the first embodiment, as shown in the enlarged schematic partial end view of FIG. 2, the substrate 20 and the partition walls 2 formed on the substrate 20 are shown.
1. A phosphor layer 22 formed on the substrate 20 between the partition walls 21 and composed of a large number of phosphor particles (red light emitting phosphor layer 22
R, green light emitting phosphor layer 22G, blue light emitting phosphor layer 22
B) and a reflective film 24 formed on the phosphor layer 22. Then, the electrons emitted from the electron beam source (specifically, the electron emitting portion 15 constituting the field emission device) and passing through the reflective film 24 collide with the phosphor layer 22, whereby the phosphor layer 22 emits light. , Obtain the desired image on the outer surface of the substrate 20. Anode panel A in the first embodiment
In P, unlike the conventional anode panel, the reflective film 24 is a phosphor layer 22 composed of a large number of phosphor particles.
The reflecting film 24 has a shape that follows the unevenness of the top surface of the, and the reflective film 24 is in surface contact with the phosphor particles that form the phosphor layer 22.
That is, the portion of the phosphor particles with which the electrons collide is in contact with the reflective film 24.

In the first embodiment, the reflection film 24 also functions as an anode electrode, is in the form of a thin sheet covering the effective area, and is connected to the anode electrode control circuit 33. The reflective film 24 is made of aluminum having a thickness of about 70 nm and is provided so as to cover the partition wall 21 (FIG. 2).
And FIG. 3).

The partition wall 21, the spacer 25, and the phosphor layer 2
The arrangement state of 2 is the same as that of FIG.
A schematic partial perspective view of is similar to FIG.

The cathode panel CP is (A) the support 10
And (B) a plurality of cathode electrodes 11 formed on the support 10 and extending in the first direction, (C) an insulating layer 12 formed on the support 10 and the cathode electrode 11, and (D) insulation. A plurality of gate electrodes 13 formed on the layer 12 and extending in a second direction different from the first direction, and (E) a gate located in a region where the cathode electrode 11 and the gate electrode 13 overlap (electron emission region). First formed on the electrode 13
The opening 14A, the second opening 14B formed in the insulating layer 12 (F) and communicating with the first opening 14A, and the second opening (G).
The electron emitting portion 15 is exposed at the bottom of the opening 14B.

In the example shown in FIG. 3, the electron emitting portion 15
Is the cathode electrode 1 located at the bottom of the second opening 14B.
It is composed of a conical Spindt-type field emission device formed on the upper part of FIG. Electron emission areas corresponding to one pixel area are arranged in a two-dimensional matrix in the effective area of the cathode panel CP. Further, one pixel is composed of an electron emission region on the cathode panel side and a phosphor layer 22 on the anode panel side facing the electron emission region. In the effective area, such pixels are arranged in the order of, for example, hundreds of thousands to millions.

The projection image in the first direction and the projection image in the second direction are orthogonal to each other. Further, the cathode electrode 11 and the gate electrode 13 each have a stripe shape.

When displaying is performed in this display device, a relative negative voltage is applied to the cathode electrode 11 from the cathode electrode control circuit 31, and a relative positive voltage (several tens of volts to several tens) is applied to the gate electrode 13. 100 volt) is applied from the gate electrode control circuit 32, and the reflective film (anode electrode) 24
A positive voltage (several hundred volts to several thousands volts) higher than that of the gate electrode 13 is applied to the anode electrode control circuit 33. When displaying is performed in such a display device, for example, a scanning signal is input to the cathode electrode 11 from the cathode electrode control circuit 31, and a video signal is input to the gate electrode 13 from the gate electrode control circuit 32. On the contrary,
A video signal may be input to the cathode electrode 11 from the cathode electrode control circuit 31, and a scanning signal may be input to the gate electrode 13 from the gate electrode control circuit 32. Cathode electrode 11
An electric field generated when a voltage is applied between the gate electrode 13 and the gate electrode 13 causes electrons to be emitted from the electron emitting portion 15 based on the quantum tunnel effect, and the electrons are reflected by the reflection film (anode electrode).
It is attracted to 24, passes through the reflection film (anode electrode) 24, and collides with the phosphor layer 22. As a result, the phosphor layer 2
2 is excited and emits light, and a desired image can be obtained.

Hereinafter, the embodiment will be described with reference to FIGS. 1A to 1F which are schematic partial sectional views of the substrate and the like and FIGS. 6 to 8 which are schematic views of the processing tank and the like. A method of manufacturing the display panel (anode panel AP) of the form 1 will be described.

[Step-100] First, the partition wall 21 is formed on the substrate 20 made of a glass substrate (see FIG. 1A). The planar shape of the partition wall 21 is a lattice shape (double girder shape). Specifically, after forming a lead glass layer colored black with a metal oxide such as cobalt oxide to a thickness of about 50 μm, the lead glass layer is selectively processed by a photolithography technique and an etching technique. It is possible to obtain the partition wall 21 (see FIG. 5) having a lattice shape (double cross shape). In some cases, the low melting glass paste may be printed on the substrate 20 by a screen printing method, and then the low melting glass paste may be fired to form the partition wall, or the photosensitive polyimide resin layer may be formed. Board 20
The barrier ribs may be formed by exposing and developing the photosensitive polyimide resin layer after forming it on the entire surface of.
The size of the partition wall 21 in one pixel is about vertical × horizontal ×
The height was 200 μm × 100 μm × 50 μm. still,
It is preferable to form a black matrix (not shown) on the surface of the portion of the substrate 20 where the partition wall 21 is to be formed before forming the partition wall 21 from the viewpoint of improving the contrast of the display image.

As a method of forming the partition wall, generally, a screen printing method, a sandblast forming method, a dry film method and a photosensitive method can be exemplified. Here, the screen printing method, an opening is formed in the portion of the screen corresponding to the portion where the partition is to be formed, the partition forming material on the screen is passed through the opening using a squeegee,
In this method, a partition wall forming material layer is formed on a substrate and then the partition wall forming material layer is fired. The dry film method is a method of laminating a photosensitive film on a substrate, removing the photosensitive film at the site where the partition is to be formed by exposure and development, embedding a material for forming the partition in the opening formed by the removal, and baking the material. Is. The photosensitive film is burned and removed by firing, and the partition wall forming material embedded in the openings remains to form partition walls. The photosensitization method is a method in which a material layer for forming partition walls having photosensitivity is formed on a substrate, the material layer is patterned by exposure and development, and then baking is performed. The sandblast forming method is, for example, for forming partition walls after forming a partition forming material layer on a substrate by using a screen printing, a roll coater, a doctor blade, a nozzle discharge type coater, or the like, and drying. In this method, the material layer portion is covered with a mask layer, and then the exposed partition wall forming material layer portion is removed by a sandblast method. The partition wall can be composed of, for example, a photosensitive polyimide resin layer or a lead glass layer colored black with a metal oxide such as cobalt oxide. The planar shape of the partition wall is a lattice shape (double-column shape), that is, a shape corresponding to one pixel, for example, a shape that surrounds four sides of a phosphor layer having a substantially rectangular planar shape, or a substantially rectangular (or striped) fluorescent light. A belt-like shape (stripe shape) extending parallel to two opposing sides of the body layer can be mentioned.

As the material forming the black matrix, it is preferable to select a material that absorbs 99% or more of the light from the phosphor layer 22. Such materials include carbon, metal thin films (eg, chromium, nickel, aluminum, molybdenum, etc., or alloys thereof), metal oxides (eg, chromium oxide), metal nitrides (eg,
Materials such as chromium nitride), heat-resistant organic resin, glass paste, and glass paste containing conductive particles such as black pigment and silver. Specific examples include photosensitive polyimide resin, chromium oxide, and oxidation. A chromium / chrome laminated film can be exemplified. In the chromium oxide / chromium laminated film, the chromium film is in contact with the substrate 20. The black matrix depends on the material to be used, such as a combination of a vacuum vapor deposition method, a sputtering method and an etching method, a vacuum vapor deposition method, a sputtering method, a combination of a spin coating method and a lift-off method, a screen printing method, a lithography technology, etc. And can be formed by an appropriately selected method.

[Step-110] Next, in order to form the red light emitting phosphor layer 22R, for example, the red light emitting phosphor particles are dispersed in polyvinyl alcohol (PVA) resin and water,
Further, the red light emitting phosphor slurry to which ammonium dichromate is added is applied to the entire surface, and then the red light emitting phosphor slurry is dried. Then, the portion of the red light emitting phosphor slurry where the red light emitting phosphor layer 22R is to be formed is irradiated with ultraviolet rays from the substrate 20 side to expose the red light emitting phosphor slurry. The red light emitting phosphor slurry is gradually hardened from the substrate 20 side. The thickness of the formed red light emitting phosphor layer 22R is determined by the irradiation amount of ultraviolet rays on the red light emitting phosphor slurry. Here, for example, the thickness of the red light emitting phosphor layer 22R is set to about 8 μm by adjusting the irradiation time of the ultraviolet light to the red light emitting phosphor slurry. Then, by developing the red light emitting phosphor slurry, the red light emitting phosphor layer 22R can be formed between the predetermined partition walls 21 (see FIG. 1B). Hereinafter, the green light emitting phosphor layer 22G is formed by performing the same treatment on the green light emitting phosphor slurry, and further, the blue light emitting phosphor layer 22B is performed by performing the same treatment on the blue light emitting phosphor slurry. Are formed (see (C) of FIG. 1). The surface of the phosphor layer 22 is microscopically made uneven by a plurality of phosphor particles. The method for forming the phosphor layer is not limited to the method described above, and after sequentially applying the red phosphor slurry, the green phosphor slurry, and the blue phosphor slurry,
Each phosphor slurry may be sequentially exposed and developed to form each phosphor layer, or each phosphor layer may be formed by a screen printing method or the like.

[Step-120] After that, the substrate 20 on which the partition wall 21 and the phosphor layer 22 are formed is placed in a liquid (specifically, water) 42 filled in the processing bath 40, and the phosphor layer 2 is formed.
2 is immersed so that it faces the liquid surface side (see FIG. 6). The discharge section 41 is closed. Then, an intermediate film having a substantially flat surface is formed on the liquid surface. Specifically, an organic solvent in which the resin forming the intermediate film 23 is dissolved is dropped on the liquid surface. That is, the intermediate film material 23A for forming the intermediate film 23 is spread on the liquid surface (see FIG. 7). Subsequently, the intermediate film material 23A is dried, for example, for about 2 minutes in a state of being suspended on the liquid surface. As a result, the intermediate film material 23
A is deposited, and the intermediate film 23 is formed flat on the liquid surface. When forming the intermediate film 23, for example, the development amount of the intermediate film material 23A is adjusted so that the thickness thereof is about 30 nm.

Then, as shown in FIG. 8, the discharge section 41 is opened, and the liquid 42 is discharged from the processing tank 40 to lower the liquid level, whereby the intermediate film 23 formed on the liquid surface is a partition wall. 21 and the intermediate film 23 moves to the partition wall 21.
, And finally the intermediate film 23 comes into contact with the phosphor layer 22 and the intermediate film 23 is left on the phosphor layer 22 (see (D) of FIG. 1). The relatively flexible intermediate film 23 follows the uneven shape of the top surface of the phosphor layer 22 and covers the unevenness of the surface of the phosphor layer 22.

[Step-130] Next, the intermediate film 23 is dried. That is, the substrate 20 is taken out of the processing tank 40,
The substrate 20 is loaded into a drying furnace and dried in a predetermined temperature environment. The drying temperature of the intermediate film 23 is, for example, 30 ° C to 6 ° C.
The temperature is preferably in the range of 0 ° C., and the drying time of the intermediate film 23 is preferably in the range of, for example, several minutes to several tens of minutes. Of course, the drying time decreases as the drying temperature increases or decreases.

[Step-140] After that, the reflection film 24 is formed on the intermediate film 23. Specifically, by a vapor deposition method or a sputtering method, a reflective film 24 made of a conductive material such as aluminum and having a thickness of 70 nm is formed so as to cover the intermediate film 23.
Are formed (see (E) in FIG. 1). The reflection film 24 has an uneven shape corresponding to the unevenness of the intermediate film 23 as the base.

[Step-150] Next, the intermediate film 23 is baked at about 400 ° C. (see FIG. 1F). By this baking treatment, the intermediate film 23 is burned and burned off, and the reflective film 24
Are left on the phosphor layer 22 and the partition wall 21. In this way, the anode panel AP can be completed. At this time, the reflection film 24 has a shape that follows the uneven shape of the top surface of the phosphor layer 22, and it is possible to obtain a state in which the portions of the phosphor particles with which the electrons collide are in contact with the reflection film. It is possible to reliably prevent the occurrence of local deterioration of the. The gas generated by the combustion of the intermediate film 23 is discharged to the outside through, for example, fine holes formed in a region of the reflective film 24 that is bent along the shape of the partition wall 21.
Since the holes are minute, they do not seriously affect the structural strength and image display characteristics of the reflective film 24.

[Step-160] A cathode panel CP having a field emission device is prepared. Cathode panel CP
Will be described in detail later. Then, the display device is assembled. Specifically, for example, the spacer 25 is attached to the cathode panel CP, the anode panel AP and the cathode panel CP are arranged so that the phosphor layer 22 and the field emission device face each other, and the anode panel AP and the cathode panel CP ( More specifically, the substrate 20 and the support 10) are made of ceramics or glass and have a height of about 1 mm.
It joins in the peripheral part via the frame body 30 of. At the time of joining, frit glass is applied to the joining portion between the frame body 30 and the anode panel AP and the joining portion between the frame body 30 and the cathode panel CP, and the anode panel AP, the cathode panel CP and the frame body 30 are attached. After combining and drying the frit glass by preliminary firing, 10 ~ 10 at 450 ° C
Main baking is performed for 30 minutes. Then, a space surrounded by the anode panel AP, the cathode panel CP, the frame body 30, and the frit glass (not shown) is provided with a through hole (not shown).
Then, the chip tube (not shown) is evacuated, and when the pressure in the space reaches about 10 ⁻⁴ Pa, the chip tube is sealed by heating and melting. In this way, the space surrounded by the anode panel AP, the cathode panel CP, and the frame body 30 can be evacuated. Alternatively, for example, the frame body 30, the anode panel AP, and the cathode panel CP may be bonded together in a high vacuum atmosphere. Alternatively, depending on the structure of the display device, the anode panel AP and the cathode panel CP may be bonded to each other only by the adhesive layer without a frame. After that, wiring connection with necessary external circuits is performed to complete the display device.

When the cathode panel CP and the anode panel AP are joined at their peripheral portions, the joining may be performed by using an adhesive layer, or, as described above, an insulating rigid material such as glass or ceramics may be used. The frame body 30 and the adhesive layer may be used together. When the frame and the adhesive layer are used together, by appropriately selecting the height of the frame, the facing distance between the cathode panel and the anode panel is set to be longer than that when only the adhesive layer is used. It is possible to Although frit glass is generally used as a constituent material of the adhesive layer, it has a melting point of 120 to 400.
A so-called low melting point metal material having a temperature of about ° C may be used. As such a low melting point metal material, In (indium: melting point 15
7 ° C); Indium-gold based low melting point alloy; Sn ₈₀ Ag
₂₀ (melting point 220 to 370 ° C), Sn ₉₅ Cu ₅ (melting point 2
27-370 ° C), etc., tin (Sn) -based high temperature solder; Pb
Lead (Pb) -based high-temperature solder such as _97.5 Ag _2.5 (melting point 304 ° C), Pb _94.5 Ag _5.5 (melting point 304 to 365 ° C), Pb _97.5 Ag _1.5 Sn _1.0 (melting point 309 ° C); Zn ₉₅ A
Zinc (Zn) -based high temperature solder such as l ₅ (melting point 380 ° C.); Sn ₅ Pb ₉₅ (melting point 300 to 314 ° C.), Sn ₂ P
Examples thereof include tin-lead standard solders such as b ₉₈ (melting point 316 to 322 ° C); brazing materials such as Au ₈₈ Ga ₁₂ (melting point 381 ° C) (the above subscripts all represent atomic%). .

Cathode panel CP and anode panel AP
When joining the three members of the frame body 30 to the frame body 30, as described above, the three members may be joined at the same time, or in the first step, either the cathode panel CP or the anode panel AP and the frame body 30 are joined. And the cathode panel CP in the second stage
Alternatively, the other side of the anode panel AP and the frame body 30 may be joined. If the three-way simultaneous bonding or the bonding in the second stage is performed in a high vacuum atmosphere, the space surrounded by the cathode panel CP, the anode panel AP, the frame body 30, and the adhesive layer becomes a vacuum at the same time as the bonding. Or after joining the three parties,
As described above, the cathode panel CP and the anode panel A
The space surrounded by P, the frame body 30, and the adhesive layer can be evacuated to create a vacuum. When exhausting is performed after joining, the pressure of the atmosphere during joining may be either normal pressure or reduced pressure, and the gas forming the atmosphere may be atmospheric air, or nitrogen gas or Group 0 of the periodic table. It may be an inert gas containing a gas belonging to (for example, Ar gas).

When the exhaust is performed after the joining, the exhaust can be performed through the tip tube previously connected to the cathode panel CP and / or the anode panel AP as described above. The tip tube is typically formed by using a glass tube, and the cathode panel CP and / or the anode panel AP is used.
Is bonded to the periphery of the through-hole provided in the ineffective region by using frit glass or the above-mentioned low melting point metal material, and after the space reaches a predetermined vacuum degree, it is completely sealed by heat fusion. It should be noted that if the entire display device is once heated and then cooled before the sealing is performed, residual gas can be released into the space, and this residual gas can be removed to the outside of the space, which is preferable. Is.

The manufacturing method of the display device (cold-cathode field emission display device) described above is summarized as follows. That is, a cold cathode field emission display comprising a cathode panel provided with a plurality of cold cathode field emission devices, and an anode panel, in which the cathode panel and the anode panel are joined at their peripheral portions via a vacuum layer. In the manufacturing method, the anode panel is (A) substrate 2
0, (B) a phosphor layer 22 made of phosphor particles and formed on the substrate 20, and (C) a reflection film 24 made of a metal thin film formed on the phosphor layer 22. A step of immersing the anode panel in (a) the substrate 20 on which the phosphor layer 22 is formed, in a liquid 42 filled in the processing bath 40 so that the phosphor layer 22 faces the liquid surface side. , (B) a step of forming the intermediate film 23 on the liquid surface,
(C) a step of leaving the intermediate film 23 on the phosphor layer 22 by discharging the liquid 42 from the treatment tank 40 and lowering the liquid level; (d) a step of drying the intermediate film 23; (e) It is manufactured through a step of forming the reflective film 24 on the intermediate film 23 and a step (f) of baking the intermediate film 23. Here, the resin forming the intermediate film 23 has a glass transition temperature of 15 ° C.
A resin of 30 ° C to 30 ° C is used.

Intermediate film material (resin) forming the intermediate film 23
As 23A, a butyl methacrylic (BMA) resin (average molecular weight 150,000) was used. In Table 1 below, the composition of the interlayer film material (resin) 23A, the glass transition temperature T _g of the BMA resin used, and the viscosity are shown as Example 1. For comparison, as an intermediate film material (resin) 23A constituting the intermediate film 23, a methacrylic copolymer resin (M
A), methyl methacrylic (MMA) resin (average molecular weight 120,000), ethyl methacrylic (EMA) resin (average molecular weight 105000), iso-butyl methacrylic (iBMA) resin (average molecular weight 30000) were used. In Table 1 below, the respective compositions of the interlayer film material (resin) 23A, the glass transition temperatures T _g and the viscosities of the used MA resin, MMA resin, EMA resin and iBMA resin are shown in Comparative Example 1 and Comparative Example 2, The results are shown as Comparative Example 3 and Comparative Example 4. In Table 1, the unit of glass transition temperature T _g is “° C”, the unit of solid content is “% by weight”, and the unit of viscosity is “N.
s / m ² ”. Further, the symbol “MT” means mineral spirits, and the symbol “EA” means ethyl alcohol.

[Table 1] Resin used Organic solvent Solid content T _g Viscosity Example 1 BMA MT 40 20 2.1 Comparative Example 1 MA MT 40 5 1.5 Comparative Example 2 MMA EA 51 35 35 5.5 Comparative Example 3 EMA Toluene 50 40 4.0 Comparative Example 4 iBMA MT 45 50 1.2

When the anode panel AP obtained in Example 1 and Comparative Examples 2 to 4 was observed with a laser microscope,
In Example 1, the reflective film 24 is not lifted from the phosphor layer 22, and the reflective film 24 has a shape that follows the uneven shape of the top surface of the phosphor layer 22, and the portion of the phosphor particle with which electrons collide. Was in contact with the reflective film. On the other hand, in Comparative Examples 2 to 4, the reflective film 24 was lifted from the phosphor layer 22. That is, the portions of the phosphor particles with which the electrons collide were not in sufficient contact with the reflective film. This rise is caused by the results of Comparative Example 2, Comparative Example 3,
The number tended to increase in the order of Comparative Example 4. That is, the higher the glass transition temperature T _g , the more the reflective film 24 floated up from the phosphor layer 22. The above results are summarized in Table 2 below. Moreover, in Comparative Example 1,
The intermediate film material was too viscous to form an intermediate film on the liquid surface. In these comparative examples, the glass transition temperature of the resin forming the interlayer film is 15 ° C.
Less than or more than 30 ° C acrylic resin (M
(MA, EMA, etc.) was used, but when these acrylic resins having a glass transition temperature of 15 ° C. to 30 ° C. were used, the same results as in the example could be obtained. Table 3 shows the values of S ₁ / S ₀ .

[0060] [Table 2]           Properties of interlayer film Shape of reflective film Example 1 Soft film as compared with Comparative Example 2 State in which the film was in sufficient contact with phosphor particles Comparative Example 1 Difficult to form a film The adhesive film could not form a reflective film Comparative Example 2 Softer film than Comparative Example 3 Partial non-contact with phosphor particles Comparative Example 3 Hard and smooth film Same as above (more non-contact than Comparative Example 2) Comparative Example 4 Very hard and smooth film State in which there is almost no contact with phosphor particles

[0061]

A substrate of phosphor particles in contact with the reflective film
The area of the projected image in the normal direction is S ₀, Of the phosphor particles
The contact area with the reflective film is S₁Then, in Example 1,
1.9 ≦ S₁/ S₀Was satisfied. On the other hand, in Comparative Example 4
Is S₁/ S₀The value of was only about 1.0.

A modified example of the arrangement of the partition walls 21, the spacers 25 and the phosphor layer 22 in the display panel corresponding to the anode panel is schematically shown in the layout diagram of FIG. In this example, the partition wall 21 has a substantially rectangular planar shape as the phosphor layer 22.
Has a strip shape (parallel to the two sides facing each other). The phosphor layer 22 may have a stripe shape extending in the vertical direction of FIG.

A schematic partial end view of a modified example of the display panel (anode panel) is shown in FIGS.

In the example shown in FIG. 10A, FIG.
In addition to the structure shown in FIG.
And a second reflective film 26 provided in a state of being supported by the second reflective film 26. Such a structure is, for example, the first embodiment.
After performing [Step-100] to [Step-150] of the manufacturing method of Step 1, again, [Step-120] to [Step-150]
Can be obtained by executing By adopting the configuration shown in FIG. 10A, it is possible to more effectively reflect the light emitted from the phosphor layer 22 to the outside. The second reflective film 26 preferably has a substantially flat surface. That is, it is preferable to have a substantially mirror surface.

[Step-120] to [Step-1]
50], the glass transition temperature T _g of the intermediate film material 23A used is not limited to 15 ° C to 30 ° C. That is, a conventionally used interlayer film material can be used. Specifically, a lacquer can be used as the interlayer film material. Here, the lacquer is a kind of varnish in a broad sense, and is a cellulose derivative, generally a mixture of nitrocellulose as a main component dissolved in a volatile solvent such as a lower fatty acid ester, or another synthetic polymer. The urethane lacquer and acrylic lacquer used are included.

The second reflective film 26 is formed by adjusting the hardness of the intermediate film for forming the second reflective film 26 and the drying time and the drying temperature of the intermediate film.
Without contacting the portion of the reflective film 24 located above
Can be formed.

Further, such a second reflective film 26 can be applied to the method of manufacturing a display panel in the third embodiment described below.

In the example shown in FIG. 10B, an anode electrode 27 is formed between the phosphor layer 22 and the substrate 20 in addition to the reflection film 24. The anode panel having such a structure can be manufactured by the [Process-1 of the manufacturing method of the first embodiment.
00], the anode electrode 27 may be previously formed on the substrate 20 before the partition wall 21 is formed. Partition 2
Depending on the shape of No. 1, the anode electrode 27 may be formed after the partition wall 21 is formed. The anode panel having such a structure can be applied to the anode panel described in FIG. 10A, and the display of the second embodiment described with reference to FIG. The present invention can be applied to the manufacturing method of the display panel as well as to the manufacturing method of the display panel in the third embodiment described below.

(Embodiment 2) Embodiment 2 is a modification of the manufacturing method of the display panel of Embodiment 1. In the second embodiment, an anode panel having the structure shown in FIG. 11 is manufactured. In the anode panel having the structure shown in FIG. 11, the second reflective film 26A is attached to the top surface of the partition wall in the anode panel described in the first embodiment. By adopting such a configuration, it is possible to more effectively reflect the light emitted from the phosphor layer toward the outside. Hereinafter, the manufacturing method of the second embodiment will be described.

[Step-200] First, in the same manner as in [Step-100] to [Step-150] of the first embodiment, the partition wall 21 and the phosphor layer 22 are formed on the substrate 20, and the reflection is performed. The film 24 is formed.

[Step-210] For example, a roll of metal foil such as lined aluminum foil or chrome foil is prepared. Then, for example, a roll coater is used to apply an adhesive to the portion of the reflective film 24 located on the top surface of the partition wall 21, and then a metal roller is used to apply a metal foil to the reflective film 24 located on the top surface of the partition wall. After being pressure-bonded to the part, the adhesive is cured. As a result, the second reflective film 26A having a substantially flat surface, that is, having a substantially mirror surface can be attached to the portion of the reflective film 24 located on the top surface of the partition wall 21. Incidentally, as the adhesive, it is preferable to select an adhesive that does not emit gas or emits little gas when placed in a vacuum atmosphere after curing.

The method of forming the second reflective film 26A in the method of manufacturing a display panel according to the second embodiment can be applied to the method of manufacturing a display panel according to the third embodiment described below.

(Embodiment 3) Embodiment 3 relates to a method of manufacturing a display panel according to a second aspect of the present invention, and more specifically, a cold cathode field emission display device (display device). The present invention relates to a method for manufacturing a display panel corresponding to the constituent anode panel.

The structures of the display panel (anode panel AP) and the display device of the third embodiment are the same as the structures of the display panel (anode panel AP) and the display device described in the first embodiment. Therefore, detailed description is omitted.

The method of manufacturing the display panel according to the third embodiment will be described below.

[Step-300] First, the same steps as [Step-100] and [Step-110] of the first embodiment are executed.

[Step-310] Next, water is sprinkled on the surface of the substrate having the phosphor layer formed thereon to form a thin film of water on the entire surface. Then, the substrate is rotated to remove unnecessary water. The phosphor layer is thinly covered with a thin film of water.

[Step-320] Then, the organic solvent in which the resin forming the intermediate film is dissolved is sprayed onto the thin film made of water. Specifically, the intermediate film material of Example 1 is sprayed to form an intermediate film on the thin film made of water.
The thin film of water is then evaporated, leaving the intermediate film on the phosphor layer. The relatively flexible intermediate film follows the uneven shape of the top surface of the phosphor layer and covers the unevenness of the surface of the phosphor layer.

[Step-330] Then, the same steps as [Step-140] and [Step-150] of the first embodiment are executed. That is, the reflective film is formed on the intermediate film. The reflection film has an uneven shape corresponding to the unevenness of the intermediate film which is the base. Then, the intermediate film is baked at about 400 ° C. At this time, the reflection film has a shape that follows the uneven shape of the top surface of the phosphor layer, and it is possible to obtain a state in which the portion of the phosphor particle with which electrons collide is in contact with the reflection film. It is possible to reliably prevent the occurrence of mechanical deterioration. After that, the display device is completed by performing the same process as the [process-160] of Embodiment 1.

The manufacturing method of the display device (cold-cathode field emission display device) described above is summarized as follows. That is, a cold cathode field emission display comprising a cathode panel provided with a plurality of cold cathode field emission devices, and an anode panel, in which the cathode panel and the anode panel are joined at their peripheral portions via a vacuum layer. In the manufacturing method, the anode panel is (A) substrate 2
0, (B) a phosphor layer 22 made of phosphor particles and formed on the substrate 20, and (C) a reflection film 24 made of a metal thin film formed on the phosphor layer 22. The step of: (a) spraying water on the surface of the substrate 20 on which the phosphor layer 22 is formed to form a thin film made of water on the entire surface; A step of forming the film 23, and a step (c) of evaporating a thin film of water to leave the intermediate film 23 on the phosphor layer 22.
(D) a step of forming the reflective film 24 on the intermediate film 23,
(E) The step of firing the intermediate film 23 is performed. Here, as the resin forming the intermediate film 23, a resin having a glass transition temperature of 15 ° C. to 30 ° C. is used.

(Fourth Embodiment) In the fourth embodiment, various field emission devices and manufacturing methods thereof will be described.

A cold cathode field electron emission device (hereinafter, abbreviated as field emission device) which constitutes a so-called three-electrode type cold cathode field emission device (hereinafter, abbreviated as display device) has a structure of an electron emission portion. Specifically, for example, the following 2
It can be divided into two categories. That is, the field emission device having the first structure includes (a) a stripe-shaped cathode electrode provided on the support and extending in the first direction, and (b) an insulation formed on the support and the cathode electrode. Layers and (c)
A stripe-shaped gate electrode provided on the insulating layer and extending in a second direction different from the first direction; (d) a first opening provided in the gate electrode; and provided in the insulating layer,
The second electron emitting portion, which is in communication with the first opening, and (e) the electron emitting portion provided on the cathode electrode located at the bottom of the second opening, and the electron emission exposed at the bottom of the second opening. It has a structure in which electrons are emitted from the part.

As the field emission device having such a first structure, the above-mentioned Spindt type (the field emission device in which the conical electron emission portion is provided on the cathode electrode located at the bottom of the second opening) is used. , A flat type (a field emission device in which a substantially flat electron-emitting portion is provided on the cathode electrode located at the bottom of the second opening).

The field emission device of the second structure is formed on (a) a striped cathode electrode provided in the support and extending in the first direction, and (b) formed on the support and the cathode electrode. An insulating layer, (c) a stripe-shaped gate electrode provided on the insulating layer and extending in a second direction different from the first direction, and (d) a first opening provided in the gate electrode,
And a second opening provided in the insulating layer and communicating with the first opening, and the portion of the cathode electrode exposed at the bottom of the second opening corresponds to the electron emitting portion. It has a structure in which electrons are emitted from the portion of the cathode electrode exposed at the bottom.

As a field emission device having such a second structure, there may be mentioned a flat type field emission device which emits electrons from the flat surface of the cathode electrode.

In the Spindt-type field emission device, as the material forming the electron emission portion, tungsten, tungsten alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, niobium, niobium alloy, tantalum, tantalum alloy, chromium, chromium are used. At least one material selected from the group consisting of alloys and silicon containing impurities (polysilicon or amorphous silicon) can be mentioned. The electron emitting portion of the Spindt-type field emission device can be formed by, for example, a vacuum vapor deposition method, a sputtering method, or a CVD method.

In the flat-type field emission device, it is preferable that the electron emitting portion is made of a material having a work function Φ smaller than that of the cathode electrode. What kind of material is selected. It may be determined based on the work function of the material forming the cathode electrode, the potential difference between the gate electrode and the cathode electrode, the required emission electron current density, and the like. Typical materials forming the cathode electrode in the field emission device include tungsten (Φ = 4.55 eV) and niobium (Φ = 4.02 to 4.8).
7 eV), molybdenum (Φ = 4.53 to 4.95 e)
V), aluminum (Φ = 4.28 eV), copper (Φ =
Examples are 4.6 eV), tantalum (Φ = 4.3 eV), chromium (Φ = 4.5 eV), and silicon (Φ = 4.9 eV). The electron emitting portion preferably has a work function Φ smaller than those materials, and its value is preferably about 3 eV or less. Such materials include carbon (Φ <1 eV), cesium (Φ = 2.14)
eV), LaB ₆ (Φ = 2.66 to 2.76 eV), B
aO (Φ = 1.6 to 2.7 eV), SrO (Φ = 1.2)
5 to 1.6 eV), Y ₂ O ₃ (Φ = 2.0 eV), CaO
(Φ = 1.6 to 1.86 eV), BaS (Φ = 2.05
eV), TiN (Φ = 2.92 eV), ZrN (Φ =
2.92 eV) can be illustrated. It is more preferable to form the electron emitting portion from a material having a work function Φ of 2 eV or less. The material forming the electron emitting portion is
It does not necessarily have to have conductivity.

Alternatively, in the flat type field emission device, as a material forming the electron emitting portion, 2 of such materials is used.
The secondary electron gain δ is 2 of the conductive material that constitutes the cathode electrode.
You may select suitably from the material which becomes larger than the secondary electron gain (delta). That is, silver (Ag), aluminum (A
l), gold (Au), cobalt (Co), copper (Cu), molybdenum (Mo), niobium (Nb), nickel (N
i), platinum (Pt), tantalum (Ta), tungsten (W), zirconium (Zr), and other metals; silicon (S
i), semiconductors such as germanium (Ge); inorganic simple substances such as carbon and diamond; and aluminum oxide (Al
₂ O ₃ ), barium oxide (BaO), beryllium oxide (B
eO), calcium oxide (CaO), magnesium oxide (MgO), tin oxide (SnO ₂ ), barium fluoride (B
It can be appropriately selected from compounds such as aF ₂ ) and calcium fluoride (CaF ₂ ). The material forming the electron emitting portion does not necessarily have to be conductive.

In the flat field emission device, carbon, more specifically, diamond, graphite, or a carbon / nanotube structure can be mentioned as a particularly preferable material for the electron emitting portion. When the electron emitting portion is composed of these, the emitted electron current density required for the display device can be obtained at an electric field intensity of 5 × 10 ⁷ V / m or less. Further, since diamond is an electric resistor, it is possible to make the emitted electron currents obtained from the respective electron emitting portions uniform, and therefore it is possible to suppress the variation in luminance when incorporated in a display device. Furthermore, since these materials have extremely high resistance to the sputtering action by the ions of the residual gas in the display device, the life of the field emission device can be extended.

Specific examples of the carbon nanotube structure include carbon nanotubes and / or carbon nanofibers. More specifically, the electron emitting portion may be composed of carbon nanotubes, the electron emitting portion may be composed of carbon nanofibers, or the electron emitting portion may be composed of a mixture of carbon nanotubes and carbon nanofibers. You may comprise a part. Macroscopically, carbon nanotubes and carbon nanofibers may be in the form of powder or thin film, and in some cases, the carbon nanotube structure has a conical shape. May be. Carbon nanotubes and carbon nanofibers can be produced by the known arc discharge method or laser ablation method.
VD method, plasma CVD method, laser CVD method, thermal CVD
It can be manufactured and formed by various CVD methods such as a CVD method, a vapor phase synthesis method, and a vapor phase growth method.

A method in which a flat field emission device, in which a carbon nanotube structure is dispersed in a binder material, is applied to a desired region of a cathode electrode, for example, and then the binder material is baked or cured (more specifically, Is a dispersion of the carbon / nanotube structure in an organic binder material such as an epoxy resin or an acrylic resin or an inorganic binder material such as water glass. It can also be manufactured by a method of removing and baking and curing the binder material.
Such a method is referred to as a first method of forming a carbon nanotube structure. As a coating method, a screen printing method can be exemplified.

Alternatively, the flat-type field emission device can be manufactured by a method of coating a metal compound solution in which a carbon nanotube structure is dispersed on a cathode electrode, and then calcining the metal compound. The carbon / nanotube structure is fixed on the surface of the cathode electrode by a matrix containing metal atoms constituting a metal compound. Such a method is referred to as a second carbon nanotube structure forming method. The matrix is preferably made of a conductive metal oxide, and more specifically, tin oxide, indium oxide, indium oxide-
It is preferably composed of tin, zinc oxide, antimony oxide, or antimony-tin oxide. After firing, it is possible to obtain a state in which a part of each carbon / nanotube structure is embedded in a matrix, or a state in which each carbon / nanotube structure is entirely embedded in a matrix. The volume resistivity of the matrix is preferably 1 × 10 ⁻⁹ Ω · m to 5 × 10 ⁻⁶ Ω · m.

Examples of the metal compound constituting the metal compound solution include an organic metal compound, an organic acid metal compound, and a metal salt (eg, chloride, nitrate, acetate). As an organic acid metal compound solution, an organic tin compound, an organic indium compound, an organic zinc compound, and an organic antimony compound are dissolved in an acid (for example, hydrochloric acid, nitric acid, or sulfuric acid), and this is dissolved in an organic solvent (for example, toluene,
Examples include those diluted with butyl acetate and isopropyl alcohol. Further, as the organic metal compound solution, an organic tin compound, an organic indium compound, an organic zinc compound, an organic antimony compound dissolved in an organic solvent (for example, toluene, butyl acetate, isopropyl alcohol) can be exemplified. When the solution is 100 parts by weight, the carbon / nanotube structure has 0.001
It is preferable that the composition contains -20 parts by weight and 0.1-10 parts by weight of the metal compound. The solution may contain a dispersant and a surfactant. From the viewpoint of increasing the thickness of the matrix, an additive such as carbon black may be added to the metal compound solution. In some cases, water may be used as a solvent instead of the organic solvent.

As a method of applying the metal compound solution in which the carbon nanotube structure is dispersed on the cathode electrode, a spray method, a spin coating method, a dipping method, a die quarter method, and a screen printing method can be exemplified. Among them, the spray method is preferable from the viewpoint of easy coating.

The metal compound solution in which the carbon nanotube structure is dispersed is applied on the cathode electrode, and then the metal compound solution is dried to form a metal compound layer. Then, an unnecessary portion of the metal compound layer on the cathode electrode is formed. After removing the metal compound, the metal compound may be baked, or after the metal compound is baked, an unnecessary portion on the cathode electrode may be removed, or the metal compound solution may be applied only on a desired region of the cathode electrode. You may.

The firing temperature of the metal compound is, for example, a temperature at which the metal salt is oxidized to form a conductive metal oxide, or the organometallic compound or the organic acid metal compound is decomposed to give an organometallic compound. The temperature may be any temperature at which a matrix containing a metal atom constituting the organic acid metal compound (for example, a metal oxide having conductivity) can be formed, and for example, it is preferably 300 ° C. or higher. The upper limit of the firing temperature may be set to a temperature at which the field emission device or the constituent element of the cathode panel is not thermally damaged.

In the first forming method or the second forming method of the carbon nanotube structure, a kind of activation treatment (cleaning treatment) is performed on the surface of the electron emitting portion after the formation of the electron emitting portion. Is preferable from the viewpoint of further improving the efficiency of electron emission from the electron emission portion. As such a treatment, hydrogen gas, ammonia gas, helium gas,
Plasma treatment in a gas atmosphere of argon gas, neon gas, methane gas, ethylene gas, acetylene gas, nitrogen gas and the like can be mentioned.

In the first forming method or the second forming method of the carbon nanotube structure, the electron emitting portion is formed on the surface of the portion of the cathode electrode located at the bottom of the second opening. It may be formed so as to extend from the portion of the cathode electrode located at the bottom of the second opening to the surface of the portion of the cathode electrode other than the bottom of the second opening. Further, the electron emitting portion may be formed on the entire surface of the portion of the cathode electrode located at the bottom of the second opening or may be formed partially.

As materials for forming cathode electrodes in various field emission devices, tungsten (W), niobium (Nb), tantalum (Ta), titanium (Ti), molybdenum (Mo), chromium (Cr), aluminum (A).
l), copper (Cu), gold (Au), silver (Ag), and other metals;
Alloys or compounds containing these metal elements (eg T
nitrides such as iN, WSi ₂ , MoSi ₂ , TiSi ₂ ,
Examples thereof include silicide such as TaSi ₂ ); semiconductor such as silicon (Si); carbon thin film such as diamond; ITO (indium / tin oxide). It is desirable that the thickness of the cathode electrode is approximately 0.05 to 0.5 μm, preferably 0.1 to 0.3 μm, but the thickness is not limited to this range.

Tungsten (W), Niobium (Nb), Tantalum (Ta), Titanium (Ti), Molybdenum (Mo), Chromium (Cr), Aluminum is used as a conductive material forming a gate electrode in various field emission devices. (A
l), copper (Cu), gold (Au), silver (Ag), nickel (Ni), cobalt (Co), zirconium (Zr),
At least one metal selected from the group consisting of iron (Fe), platinum (Pt), and zinc (Zn); alloys or compounds containing these metal elements (for example, nitrides such as TiN, WSi ₂ , MoSi ₂₎ , TiSi ₂ , TaSi ₂ or the like); or a semiconductor such as silicon (Si);
Examples thereof include conductive metal oxides such as ITO (indium tin oxide), indium oxide, and zinc oxide.

As the method of forming the cathode electrode and the gate electrode, for example, an evaporation method such as an electron beam evaporation method or a hot filament evaporation method, a sputtering method, a CVD method, a combination of an ion plating method and an etching method, a screen printing method, a plating method. Method, lift-off method and the like. By the screen printing method or the plating method, it is possible to directly form, for example, a stripe-shaped cathode electrode.

In the field emission device having the first structure or the second structure, depending on the structure of the field emission device, the inside of the first opening and the second opening provided in the gate electrode and the insulating layer. There may be one electron-emitting portion in the gate electrode, a plurality of electron-emitting portions in the first opening and the second opening provided in the gate electrode and the insulating layer, or the gate electrode. A plurality of first openings are provided in the insulating layer, one second opening communicating with the first opening is provided in the insulating layer, and one or a plurality of electron emitting portions is provided in the one second opening provided in the insulating layer. May exist.

The planar shape of the first opening or the second opening (the shape when the opening is cut by a virtual plane parallel to the surface of the support) is circular, elliptical, rectangular, polygonal, or rounded. Any shape such as a rectangle or a rounded polygon can be used. The first opening can be formed by, for example, isotropic etching, a combination of anisotropic etching and isotropic etching, or depending on the method of forming the gate electrode, the first opening can be formed. It can also be formed directly. The formation of the second opening is also performed by, for example, isotropic etching,
It can be performed by a combination of anisotropic etching and isotropic etching.

In the field emission device having the first structure, a resistor layer may be provided between the cathode electrode and the electron emitting portion. Alternatively, when the surface of the cathode electrode corresponds to the electron emitting portion (that is, in the field emission device having the second structure), the cathode electrode corresponds to the conductive material layer, the resistor layer, and the electron emitting portion. The electron-emitting layer may have a three-layer structure. By providing the resistor layer, it is possible to stabilize the operation of the field emission device and make the electron emission characteristics uniform. Carbon materials such as silicon carbide (SiC) and SiCN are used as materials for forming the resistor layer,
Examples thereof include semiconductor materials such as SiN and amorphous silicon, and refractory metal oxides such as ruthenium oxide (RuO ₂ ), tantalum oxide and tantalum nitride. Examples of the method for forming the resistor layer include a sputtering method, a CVD method, and a screen printing method. The resistance value may be approximately 1 × 10 ⁵ to 1 × 10 ⁷ Ω, preferably several MΩ.

As a constituent material of the insulating layer, SiO ₂ , BP is used.
SG, PSG, BSG, AsSG, PbSG, SiN,
SiON, SOG (spin on glass), low melting point glass, SiO ₂ based materials such as glass paste, SiN,
Insulating resins such as polyimide can be used alone or in appropriate combination. To form the insulating layer, use CV
Known processes such as D method, coating method, sputtering method and screen printing method can be used.

[Spint-type field emission device] The Spindt-type field emission device is (a) the first
A striped cathode electrode 11 extending in the direction of
(B) An insulating layer 12 formed on the support 10 and the cathode electrode 11, and (c) a stripe-shaped gate electrode 13 provided on the insulating layer 12 and extending in a second direction different from the first direction. And (d) the first electrode provided on the gate electrode 13.
Electrons provided on the opening 14A and the second opening 14B provided in the insulating layer 12 and communicating with the first opening 14A, and (e) on the cathode electrode 11 located at the bottom of the second opening 14B. The electron emission portion 15 has a structure in which electrons are emitted from the conical electron emission portion 15 exposed at the bottom of the second opening 14B.

A method of manufacturing a Spindt-type field emission device will be described below with reference to FIGS. ) And (B).

The Spindt-type field emission device can be basically obtained by a method of forming the conical electron emission portion 15 by vertical vapor deposition of a metal material. That is,
The vapor deposition particles enter the first opening 14A provided in the gate electrode 13 perpendicularly, but by utilizing the shielding effect of the overhang-like deposit formed near the opening end of the first opening 14A The amount of vapor deposition particles reaching the bottom of the second opening 14B is gradually reduced to form the electron emitting portion 15 which is a conical deposit in a self-aligned manner. Here, a method of forming the separation layer 16 on the gate electrode 13 and the insulating layer 12 in advance in order to facilitate the removal of unnecessary overhang-like deposits will be described. 12 to 17, only one electron emitting portion is shown.

[Step-A0] First, for example, a glass substrate
On a support 10 made of, for example, polysilicon
Conductive material layer for cathode electrode is formed by plasma CVD method
After that, apply lithography technology and dry etching technology
Patterning the conductive material layer for the cathode electrode based on
The striped cathode electrode 11 is formed. afterwards,
SiO on the entire surface ₂An insulating layer 12 composed of
To do.

[Step-A1] Next, a conductive material layer for a gate electrode (for example, a TiN layer) is formed on the insulating layer 12 by a sputtering method, and then a conductive material layer for a gate electrode is formed by a lithographic technique and By patterning with a dry etching technique, the stripe-shaped gate electrode 13 can be obtained. Striped cathode electrode 11
Extends in the left-right direction of the drawing and the stripe-shaped gate electrode 13 extends in the direction perpendicular to the drawing.

The gate electrode 13 is formed of P by vacuum vapor deposition or the like.
A known thin film forming technique such as a VD method, a CVD method, a plating method such as an electroplating method or an electroless plating method, a screen printing method, a laser ablation method, a sol-gel method, a lift-off method, and an etching technology as necessary It may be formed by a combination. According to the screen printing method or the plating method, it is possible to directly form, for example, a stripe-shaped gate electrode.

[Step-A2] After that, the resist layer is formed again, the first opening 14A is formed in the gate electrode 13 by etching, and the second opening 14B is formed in the insulating layer, and the second opening is formed. After exposing the cathode electrode 11 to the bottom of 14B, the resist layer is removed. Thus, FIG.
The structure shown in (A) of 2 can be obtained.

[Step-A3] Next, the peeling layer 16 is formed by obliquely depositing nickel (Ni) on the insulating layer 12 including the gate electrode 13 while rotating the support 10 (see FIG. 12). (See (B)). At this time, the support 10
By selecting a sufficiently large incident angle of the vapor deposition particles with respect to the normal line (for example, the incident angle is 65 degrees to 85 degrees), the second
The peeling layer 16 can be formed on the gate electrode 13 and the insulating layer 12 with almost no nickel deposited on the bottom of the opening 14B. The release layer 16 has the first opening 14
It projects like an eaves from the opening end of A, and the diameter of the first opening 14A is substantially reduced.

[Step-A4] Next, for example, molybdenum (Mo) as a conductive material is vertically vapor-deposited on the entire surface (incidence angle 3).
10 degrees). At this time, as shown in FIG. 13A, as the conductive material layer 17 having the overhang shape grows on the peeling layer 16, the substantial diameter of the first opening 14A is gradually reduced. The vapor deposition particles that contribute to the deposition at the bottom of the second opening 14B are gradually limited to those that pass near the center of the first opening 14A. As a result, a conical deposit is formed on the bottom of the second opening 14B, and this conical deposit is used as the electron emitting portion 15.
Becomes

[Step-A5] After that, as shown in FIG. 13B, the peeling layer 16 is peeled from the surfaces of the gate electrode 13 and the insulating layer 12 by the lift-off method, and the gate electrode 13 is removed.
And the conductive material layer 17 above the insulating layer 12 is selectively removed. Thus, a cathode panel having a plurality of Spindt-type field emission devices can be obtained.

[Flat-type field emission device (1)] The flat-type field emission device includes (a) a cathode electrode 11 provided on the support 10 and extending in the first direction, and (b) the support 1.
0 and the insulating layer 12 formed on the cathode electrode 11,
(C) A gate electrode 13 provided on the insulating layer 12 and extending in a second direction different from the first direction, (d) a first opening 14A provided in the gate electrode 13, and the insulating layer 1
Second opening 14B provided in the second opening 14B and communicating with the first opening 14A, and (e) a flat electron-emitting portion 15 provided on the cathode electrode 11 located at the bottom of the second opening 14B.
A has a structure in which electrons are emitted from the electron emitting portion 15A exposed at the bottom of the second opening 14B.

The electron emitting portion 15A includes a matrix 18,
And a carbon nanotube structure (specifically, the carbon nanotube 19) embedded in the matrix 18 in a state where the tip portion protrudes, and the matrix 18 is made of a metal oxide having conductivity (specifically, Is
Indium-tin oxide, ITO).

Hereinafter, a method of manufacturing a field emission device will be described with reference to FIG.
(A) and (B) of FIG. 15 and (A) and (B) of FIG.

[Step-B0] First, a striped cathode electrode made of a chromium (Cr) layer having a thickness of about 0.2 μm formed on the support 10 made of, for example, a glass substrate by, for example, a sputtering method and an etching technique. 11
To form.

[Step-B1] Next, a metal compound solution containing an organic acid metal compound in which the carbon nanotube structure is dispersed is applied onto the cathode electrode 11 by, for example, a spray method. Specifically, the metal compound solutions exemplified in Table 4 below are used. Incidentally, in the metal compound solution, the organic tin compound and the organic indium compound are in a state of being dissolved in an acid (for example, hydrochloric acid, nitric acid, or sulfuric acid). Carbon nanotubes are manufactured by an arc discharge method and have an average diameter of 30 nm and an average length of 1 μm. Upon coating, the support is heated to 70 to 150 ° C.
The coating atmosphere is an air atmosphere. After coating, the support is heated for 5 to 30 minutes to evaporate butyl acetate sufficiently.
Thus, by heating the support during coating,
Place the carbon nanotubes on the surface of the cathode electrode in a state where the carbon nanotubes are not horizontal as a result of the drying of the coating solution before self-leveling the carbon nanotubes toward the horizontal direction of the surface of the cathode electrode be able to. That is, it is possible to orient the carbon nanotubes in a state where the tips of the carbon nanotubes face the direction of the anode electrode, in other words, the carbon nanotubes are closer to the normal direction of the support.
A metal compound solution having the composition shown in Table 4 may be prepared in advance, or a metal compound solution containing no carbon nanotubes may be prepared in advance, and the carbon nanotubes and the metal compound may be prepared before coating. You may mix with a solution. Further, in order to improve the dispersibility of the carbon nanotubes, ultrasonic waves may be applied during the preparation of the metal compound solution.

[0122] [Table 4] Organic tin compound and organic indium compound: 0.1 to 10 parts by weight Dispersant (sodium dodecyl sulfate): 0.1 to 5 parts by weight Carbon nanotube: 0.1 to 20 parts by weight Butyl acetate: Residual

When the organic acid metal compound solution used is an organic tin compound dissolved in an acid, tin oxide is obtained as a matrix, and the organic indium compound dissolved in an acid is used, indium oxide is used as a matrix. Is obtained, if the one obtained by dissolving the organic zinc compound in an acid is used, zinc oxide is obtained as the matrix, and if the one obtained by dissolving the organic antimony compound in the acid is used, antimony oxide is obtained as the matrix, and the organic antimony compound and When an organic tin compound dissolved in an acid is used, antimony-tin oxide can be obtained as a matrix. When an organotin compound is used as the organometallic compound solution, tin oxide is obtained as a matrix, when an organic indium compound is used, indium oxide is obtained as a matrix, and when an organozinc compound is used, zinc oxide is obtained as a matrix. If an organic antimony compound is used, antimony oxide is obtained as a matrix, and if an organic antimony compound and an organic tin compound are used, antimony-tin oxide is obtained as a matrix. Alternatively, a solution of metal chloride (eg, tin chloride, indium chloride) may be used.

In some cases, remarkable irregularities may be formed on the surface of the metal compound layer after drying the metal compound solution. In such a case, it is desirable to apply the metal compound solution again on the metal compound layer without heating the support.

[Step-B2] Then, the metal compound comprising the organic acid metal compound is fired to form the metal atom (specifically, In and S) constituting the organic acid metal compound.
The electron emitting portion 15A in which the carbon nanotubes 19 are fixed to the surface of the cathode electrode 11 by the matrix (specifically, metal oxide, more specifically, ITO) 18 containing n) is obtained. Firing in air atmosphere for 3
Perform at 50 ° C for 20 minutes. Thus, the volume resistivity of the obtained matrix 18 was 5 × 10 ⁻⁷ Ω · m. By using an organic acid metal compound as a starting material, even at a low temperature such as a firing temperature of 350 ° C,
A matrix 18 of ITO can be formed. Incidentally, an organic metal compound solution may be used instead of the organic acid metal compound solution, and when a metal chloride solution (for example, tin chloride or indium chloride) is used, tin chloride or indium chloride may be removed by firing. While being oxidized, the matrix 18 made of ITO is formed.

[Step-B3] Next, a resist layer is formed on the entire surface, and a circular resist layer having a diameter of, for example, 10 μm is left above the desired region of the cathode electrode 11. And
The matrix 18 is etched with hydrochloric acid at 10 to 60 ° C. for 1 to 30 minutes to remove unnecessary portions of the electron emitting portion. Further, when the carbon nanotubes are still present in a region other than the desired region, the carbon nanotubes are etched by the oxygen plasma etching treatment under the conditions exemplified in Table 5 below. The bias power is 0
Although W may be used, that is, DC may be used, but it is desirable to add bias power. The support may be heated to, for example, about 80 ° C.

[Table 5] Equipment used: RIE equipment Introduced gas: Gas containing oxygen Plasma excitation power: 500W Bias power: 0-150W Processing time: 10 seconds or more

Alternatively, the carbon nanotubes may be etched by the wet etching process under the conditions shown in Table 6.

[Table 6] Solution used: KMnO ₄ Temperature: 20 to 120 ° C Treatment time: 10 seconds to 20 minutes

After that, the structure shown in FIG. 14A can be obtained by removing the resist layer.
It is not limited to leaving a circular electron emitting portion having a diameter of 10 μm. For example, the electron emitting portion may be left on the cathode electrode 11.

[Step-B1], [Step-B3],
You may perform in order of [process-B2].

[Step-B4] Next, the electron emitting portion 15A,
An insulating layer 12 is formed on the support 10 and the cathode electrode 11. Specifically, the insulating layer 12 having a thickness of about 1 μm is formed on the entire surface by a CVD method using, for example, TEOS (tetraethoxysilane) as a source gas.

[Step-B5] Thereafter, the stripe-shaped gate electrode 13 is formed on the insulating layer 12, and the insulating layer 1 is further formed.
2 and the mask layer 118 is provided on the gate electrode 13,
A first opening 14A is formed in the gate electrode 13, and a second opening 14B communicating with the first opening 14A formed in the gate electrode 13 is further formed in the insulating layer 12 (see FIG. 14B). ). When the matrix 18 is made of a metal oxide such as ITO, the matrix 18 is not etched when the insulating layer 12 is etched. That is, the etching selection ratio between the insulating layer 12 and the matrix 18 is almost infinite. Therefore, the carbon nanotube 19 is not damaged by the etching of the insulating layer 12.

[Step-B6] Next, it is preferable to remove a part of the matrix 18 under the conditions shown in Table 7 below to obtain the carbon nanotubes 19 with the tips protruding from the matrix 18. Thus, FIG.
Thus, the electron emitting portion 15A having the structure shown in FIG.

[Table 7] Etching solution: hydrochloric acid Etching time: 10 seconds to 30 seconds Etching temperature: 10-60 ° C

The etching of the matrix 18 changes the surface state of some or all of the carbon nanotubes 19 (for example, oxygen atoms or oxygen molecules,
In some cases, fluorine atoms are adsorbed) and are inactive with respect to field emission. Therefore, after that, the electron emitting portion 15A
On the other hand, it is preferable to perform plasma treatment in a hydrogen gas atmosphere, which activates the electron emitting portion 15A and further improves the electron emission efficiency from the electron emitting portion 15A. The conditions of the plasma treatment are shown in Table 8 below.

[Table 8] Gas used: H ₂ = 100 sccm Power supply power: 1000 W Support applied power: 50 V Reaction pressure: 0.1 Pa Support temperature: 300 ° C

After that, in order to release the gas from the carbon nanotubes 19, heat treatment or various plasma treatments may be applied, or the carbon nanotubes 19 may be adsorbed to adsorb the adsorbate intentionally. The carbon nanotubes 19 may be exposed to a gas containing a desired substance. Further, in order to purify the carbon nanotubes 19, oxygen plasma treatment or fluorine plasma treatment may be performed.

[Step-B7] After that, the side wall surface of the second opening 14B provided in the insulating layer 12 is made to recede by isotropic etching, so that the opening end of the gate electrode 13 is exposed. ,preferable. The isotropic etching can be performed by dry etching that uses radicals as a main etching species, such as chemical dry etching, or wet etching that uses an etching solution. The etching liquid is, for example, 49% hydrofluoric acid aqueous solution and pure water 1: 100 (volume ratio)
Mixtures can be used. Then, the mask layer 118
To remove. Thus, the field emission device shown in FIG. 15B can be completed.

After [Step-B5], [Step-B
7] and [Step-B6] may be performed in this order.

[Flat Field Emission Device (Part 2)] A schematic partial sectional view of the flat field emission device is shown in FIG.
Shown in. This flat field emission device includes a cathode electrode 11 formed on a support 10 made of, for example, glass, a support 10 and an insulating layer 1 formed on the cathode electrode 11.
2, the gate electrode 13 formed on the insulating layer 12, the opening 14 penetrating the gate electrode 13 and the insulating layer 12 (the first opening provided in the gate electrode 13 and the first opening provided in the insulating layer 12, The second opening communicating with the first opening) and the flat electron-emitting portion (electron-emitting layer 15) provided on the portion of the cathode electrode 11 located at the bottom of the opening 14.
B). Here, the electron emission layer 15B is formed on the striped cathode electrode 11 extending in the direction perpendicular to the plane of the drawing. Further, the gate electrode 13 extends in the left-right direction of the drawing sheet. The cathode electrode 11 and the gate electrode 13 are made of chromium. Specifically, the electron emission layer 15B is composed of a thin layer made of graphite powder. In the flat-type field emission device shown in FIG. 16A, the electron emission layer 15B is formed over the entire surface of the cathode electrode 11, but the structure is not limited to this. The point is that the electron emission layer 15B may be provided at least at the bottom of the opening 14.

[Planar type field emission device] A schematic partial sectional view of a planar type field emission device is shown in FIG. 16 (B). This flat type field emission device includes a striped cathode electrode 11 formed on a support 10 made of, for example, glass.
The insulating layer 12 formed on the support 10 and the cathode electrode 11, the stripe-shaped gate electrode 13 formed on the insulating layer 12, and the first opening and the second opening penetrating the gate electrode 13 and the insulating layer 12. It comprises an opening (opening 14). The cathode electrode 11 is exposed at the bottom of the opening 14. The cathode electrode 11 extends in the direction perpendicular to the paper surface of the drawing, and the gate electrode 13 extends in the left-right direction of the paper surface of the drawing. The cathode electrode 11 and the gate electrode 13 are made of chromium (C
r) and the insulating layer 12 is made of SiO ₂ . Here, the portion of the cathode electrode 11 exposed at the bottom of the opening 14 corresponds to the electron emitting portion 15C.

Although the present invention has been described based on the embodiments of the present invention, the present invention is not limited to these. The configurations and structures of the anode panel, the cathode panel, the display device, and the field emission device described in the embodiments of the invention are examples, and can be changed as appropriate. The anode panel, the cathode panel, the display device, and the field emission device can be modified. The manufacturing method of is also an example, and can be appropriately changed. Further, various materials used in manufacturing the anode panel and the cathode panel are also examples, and can be appropriately changed. In the display device, the color display has been described as an example, but a single color display may be used.

The anode electrode may be an anode electrode of a type in which the effective area is covered with one sheet of a conductive material, or one or a plurality of electron emitting portions, or an anode electrode corresponding to one or a plurality of pixels. It may be an anode electrode in which the units are assembled. When the anode electrode has the former configuration, such an anode electrode may be connected to the anode electrode control circuit, and when the anode electrode has the latter configuration, for example, each anode electrode unit may be connected to the anode electrode control circuit.

Further, in the field emission device, one electron emission portion corresponds to one opening portion has been described. However, depending on the structure of the field emission device, a plurality of electron emission portions may be formed in one opening portion. It is also possible to adopt a configuration in which one electron emission portion corresponds to a plurality of openings or a plurality of openings. Alternatively, a plurality of first openings may be provided in the gate electrode, a plurality of second openings communicating with the plurality of first openings of the insulating layer may be provided, and one or a plurality of electron emitting portions may be provided. You can also

In the field emission device, the second insulating layer 52 is further provided on the gate electrode 13 and the insulating layer 12, and the second insulating layer 52 is formed.
The focusing electrode 53 may be provided on the insulating layer 52. FIG. 17 shows a schematic partial end view of a field emission device having such a structure. The first opening 14 is formed in the second insulating layer 52.
A third opening 54 communicating with A is provided. The converging electrode 53 is formed, for example, in [Step-A2] by forming the stripe-shaped gate electrode 13 on the insulating layer 12, forming the second insulating layer 52, and then forming the second insulating layer 52. After forming the patterned converging electrode 53, the converging electrode 53 and the third opening 54 in the second insulating layer 52.
And the first opening 14A may be further provided in the gate electrode 13. In addition, depending on the patterning of the focusing electrode,
It is also possible to use one or a plurality of electron emitting portions, or a focusing electrode of a type in which focusing electrode units corresponding to one or a plurality of pixels are assembled, or to cover the effective area with one sheet of conductive material. It is also possible to use a focusing electrode of the above type. Although the Spindt-type field emission device is shown in FIG. 17, it goes without saying that other field emission devices can be used.

The focusing electrode is formed not only by such a method, but also, for example, 42% Ni-Fe having a thickness of several tens of μm.
It is also possible to form a focusing electrode by forming an insulating film made of, for example, SiO _{2 on} both surfaces of a metal plate made of an alloy and then forming an opening by punching or etching in a region corresponding to each pixel. Then, the cathode panel, the metal plate, and the anode panel are stacked, the frame bodies are arranged on the outer peripheral portions of both panels, and heat treatment is performed, whereby the insulating film and the insulating layer 12 formed on one surface of the metal plate.
It is also possible to complete the display device by adhering and, the insulating film formed on the other surface of the metal plate and the anode panel are adhered, these members are integrated, and then vacuum-sealed.

The gate electrode may be a gate electrode of a type in which the effective region is covered with one sheet of conductive material (having an opening). In this case, a positive voltage is applied to the gate electrode. A switching element formed of, for example, a TFT is provided between the cathode electrode forming each pixel and the cathode electrode control circuit, and the operation state of the switching element controls the application state to the electron emitting portion forming each pixel. Then, the light emitting state of the pixel is controlled.

Alternatively, the cathode electrode may be a cathode electrode of a type in which the effective area is covered with one sheet of conductive material. In this case, a voltage is applied to the cathode electrode. Then, for example, a TFT is provided between the electron-emitting portion and the gate electrode control circuit which form each pixel.
Is provided, and the operation of the switching element controls the application state to the gate electrode forming each pixel, and controls the light emission state of the pixel.

The cold cathode field emission display is not limited to the so-called three-electrode type composed of the cathode electrode, the gate electrode and the anode electrode, but may be the so-called two-electrode type composed of the cathode electrode and the anode electrode. it can. FIG. 18 shows a schematic partial end view of the display device having such a structure. The partition walls are not shown in FIG. The field emission device in this display device includes a support 10
The cathode electrode 11 provided above and the cathode electrode 11
The electron emitting portion 15A is formed of the carbon nanotubes 19 formed above. The anode electrode 24A forming the anode panel AP has a stripe shape.
The structure of the electron emitting portion is not limited to the carbon nanotube structure. The projected image of the striped cathode electrode 11 and the projected image of the striped anode electrode 24A are orthogonal to each other. Specifically, the cathode electrode 11 extends in the direction perpendicular to the paper surface of the drawing, and the anode electrode 24A extends in the left-right direction of the paper surface of the drawing. In the cathode panel CP of this display device, a large number of electron emission regions formed by a plurality of field emission devices as described above are formed in a two-dimensional matrix in the effective region.

In this display device, the anode electrode 2
Based on the electric field formed by 4A, electrons are emitted from the electron emitting portion 15A based on the quantum tunnel effect, and the electrons are attracted to the anode electrode 24A, and the phosphor layer 2
Clash with 2. That is, the electron emission portion 15 located in a region (anode electrode / cathode electrode overlapping region) where the projection image of the anode electrode 24A and the projection image of the cathode electrode 11 overlap.
The display device is driven by a so-called simple matrix system in which electrons are emitted from A. Specifically, the cathode electrode control circuit 31 applies a relatively negative voltage to the cathode electrode 11, and the anode electrode control circuit 33 applies a relatively positive voltage to the anode electrode 24A. as a result,
Column-selected cathode electrode 11 and row-selected anode electrode 24A (or row-selected cathode electrode 11)
Electrons are selectively emitted into the vacuum space from the carbon nanotubes 19 forming the electron emitting portion 15A located in the anode electrode / cathode electrode overlapping region between the anode electrode 24A) and the column-selected anode electrode 24A). 24
It is attracted to A and collides with the phosphor layer 22 constituting the anode panel AP to excite the phosphor layer 22 to emit light.

The anode panel AP in the two-electrode type display device described above can have the structure described in the first embodiment or its modification, the second embodiment, and the third embodiment. It can be manufactured by the method described.

The electron emission region can also be composed of a field emission device commonly called a surface conduction type field emission device. This surface-conduction type field emission device includes, for example, tin oxide (SnO ₂ ), gold (Au), indium oxide (In ₂ O ₃ ) / tin oxide (SnO ₂ ), carbon, and palladium oxide (on a support made of glass. A pair of electrodes made of a conductive material such as PdO) having a small area and arranged with a predetermined gap (gap) formed in a matrix. A carbon thin film is formed on each electrode. The row-direction wiring is connected to one electrode of the pair of electrodes, and the column-direction wiring is connected to the other electrode of the pair of electrodes. By applying a voltage to the pair of electrodes,
An electric field is applied to the carbon thin films facing each other across the gap, and electrons are emitted from the carbon thin films. By colliding such electrons with the phosphor layer on the anode panel, the phosphor layer is excited and emits light, and a desired image can be obtained.

[0154]

In the method of manufacturing a display panel according to the present invention, the glass transition temperature of the resin constituting the intermediate film is regulated to 15 ° C to 30 ° C, whereby the portion of the phosphor particles with which electrons collide. As a result, it is possible to obtain a state in which the phosphor particles are in contact with the reflective film, and it is possible to reliably prevent local deterioration of the phosphor particles. On the other hand, in the display panel of the present invention, the occurrence of local deterioration of the phosphor particles can be reliably prevented by defining the contact area of the phosphor particles with respect to the reflective film. Therefore, it is possible to avoid the occurrence of problems such as shortening the life of the display device.

[Brief description of drawings]

1A to 1F are schematic partial end views of a substrate and the like for explaining a method for manufacturing a display panel.

FIG. 2 is a schematic end view in which a part of an anode panel, which is a display panel according to Embodiment 1 of the present invention, is enlarged.

FIG. 3 is a schematic partial end view of a cold cathode field emission display.

FIG. 4 is a schematic partial perspective view of a cathode panel that constitutes a cold cathode field emission display.

FIG. 5 is a layout diagram schematically showing the layout of partition walls, spacers, and phosphor layers in an anode panel that is a display panel that constitutes a cold cathode field emission display.

FIG. 6 is a schematic diagram for explaining the manufacturing method for the display panel in the first embodiment of the present invention.

FIG. 7 is a continuation of FIG. 6 and shows a first embodiment of the invention.
FIG. 6 is a schematic diagram for explaining the method for manufacturing the display panel in FIG.

FIG. 8 is a continuation of FIG. 7 and is a first embodiment of the invention.
FIG. 6 is a schematic diagram for explaining the method for manufacturing the display panel in FIG.

FIG. 9 is a partition in a display panel corresponding to an anode panel in a cold cathode field emission display,
It is a layout diagram which shows the modification of a layout of a spacer and a fluorescent substance layer typically.

10 (A) and 10 (B) are schematic partial end views of a modified example of a display panel corresponding to an anode panel in a cold cathode field emission display.

FIG. 11 is a schematic partial end view of a display panel corresponding to the anode panel according to the second embodiment of the invention.

12 (A) and 12 (B) are schematic partial end views of a support and the like for explaining a method of manufacturing a Spindt-type cold cathode field emission device.

13A and 13B are schematic partial views of a support and the like for explaining the method of manufacturing a Spindt-type cold cathode field emission device, following FIG. 12B. It is an end view.

14 (A) and 14 (B) are schematic partial end views of a support and the like for explaining a method of manufacturing a flat-type cold cathode field emission device (No. 1).

15A and 15B are schematic views of a support and the like for explaining the method for manufacturing the flat-type cold cathode field emission device (part 1), following FIG. 14B. It is a partial end view of FIG.

16 (A) and 16 (B) are schematic partial cross-sectional views of a flat-type cold cathode field emission device (part 2) and a flat-type cold cathode field emission device, respectively. It is a typical partial cross section figure.

FIG. 17 is a schematic partial end view of a Spindt-type cold cathode field emission device having a focusing electrode.

FIG. 18 is a schematic partial end view of a so-called two-electrode type cold cathode field emission display.

FIG. 19 is a diagram schematically showing a contact state between an anode electrode and a phosphor layer obtained by a conventional method for manufacturing an anode panel for a cold cathode field emission display.

FIG. 20 is an enlarged schematic view showing a contact state between an anode electrode obtained by a method for manufacturing an anode panel for a conventional cold cathode field emission display and phosphor particles constituting a phosphor layer. FIG.

[Explanation of symbols]

CP ... Cathode panel, AP ... Anode panel, 10 ... Support, 11 ... Cathode electrode, 12
... Insulating layer, 13 ... Gate electrode, 14 ... Opening portion, 14A ... First opening portion, 14B ... Second opening portion, 15, 15A, 15B, 15C ... Electron emission Department,
16 ... Release layer, 17 ... Conductive material layer, 18 ...
Matrix, 19 ... Carbon nanotube, 2
0 ... Substrate, 21 ... Partition wall, 22, 22R, 22
G, 22B ... Phosphor layer, 23 ... Intermediate film, 23A
... Intermediate film material, 24 ... Reflective film, 25 ... Spacer, 26, 26A ... Second reflective film, 27 ... Anode electrode, 30 ... Frame body, 31 ... Cathode electrode control circuit, 32 ... Gate electrode control circuit, 33 ...
Anode electrode control circuit, 40 ... Treatment tank, 41 ...
Discharge part, 42 ... Liquid, 52 ... Second insulating layer, 5
3 ... Focusing electrode, 54 ... Third opening

Claims (15)

[Claims] 1. A reflective film comprising: (A) a substrate; (B) a phosphor layer formed of phosphor particles on the substrate; and (C) a metal thin film formed on the phosphor layer. Which is a method for producing a display panel for obtaining a desired image by emitting electrons from an electron beam source and passing through a reflective film to collide with the phosphor layer, thereby causing the phosphor layer to emit light. And (a) a step of immersing the substrate on which the phosphor layer is formed in a liquid filled in the processing tank so that the phosphor layer faces the liquid surface side, and (b) an intermediate step on the liquid surface. A step of forming a film; (c) a step of leaving the intermediate film on the phosphor layer by discharging the liquid from the treatment tank to lower the liquid level; and (d) a step of drying the intermediate film. e) a step of forming a reflective film on the intermediate film, and (f) a step of baking the intermediate film, Method of manufacturing a display panel, wherein the glass transition temperature of the resin forming is 15 ° C to 30 ° C. 2. The method for manufacturing a display panel according to claim 1, wherein the resin forming the intermediate film is an acrylic resin. 3. The method for manufacturing a display panel according to claim 1, wherein the reflective film also functions as an anode electrode, and the display panel constitutes an anode panel of a cold cathode field emission display. . 4. An anode electrode is formed between a phosphor layer and a substrate, and the display panel constitutes an anode panel of a cold cathode field emission display device. Of manufacturing the display panel of. 5. The method of manufacturing a display panel according to claim 1, wherein the reflective film is made of aluminum or chromium. 6. A reflective film comprising: (A) a substrate; (B) phosphor particles, a phosphor layer formed on the substrate; and (C) a metal thin film formed on the phosphor layer. Which is a method for producing a display panel for obtaining a desired image by emitting electrons from an electron beam source and passing through a reflective film to collide with the phosphor layer, thereby causing the phosphor layer to emit light. And (a) a step of spraying water on the surface of the substrate on which the phosphor layer is formed to form a thin film of water on the entire surface, and (b) a step of forming an intermediate film on the thin film of water. , (C) a step of evaporating a thin film of water to leave the intermediate film on the phosphor layer, (d) a step of forming a reflective film on the intermediate film, and (e) a step of baking the intermediate film, The glass transition temperature of the resin constituting the intermediate film is 15 ° C to 30 ° C. A method of manufacturing a display panel for the butterflies. 7. The intermediate film is formed in the step (b) by spraying an organic solvent in which a resin forming the intermediate film is dissolved onto a thin film made of water. Manufacturing method of display panel. 8. The method of manufacturing a display panel according to claim 6, wherein the resin forming the intermediate film is an acrylic resin. 9. The method of manufacturing a display panel according to claim 6, wherein the reflective film also functions as an anode electrode, and the display panel constitutes an anode panel of a cold cathode field emission display. . 10. The display panel according to claim 6, wherein an anode electrode is formed between the phosphor layer and the substrate, and the display panel constitutes an anode panel of a cold cathode field emission display. Of manufacturing the display panel of. 11. The method for manufacturing a display panel according to claim 6, wherein the reflective film is made of aluminum or chromium. 12. A reflective film comprising: (A) a substrate; (B) phosphor particles, a phosphor layer formed on the substrate; and (C) a metal thin film formed on the phosphor layer. , Which is a display panel for obtaining a desired image when electrons emitted from an electron beam and passed through a reflection film collide with the phosphor layer, and the phosphor layer emits light. When the area of the projected image of the phosphor particles in contact with the substrate in the normal direction to the substrate is S ₀ , and the contact area of the phosphor particles with the reflection film is S ₁ , 1.9S ₀ ≦ S ₁ is satisfied. Characteristic display panel. 13. The display panel according to claim 12, wherein the reflective film also functions as an anode electrode, and the display panel constitutes an anode panel of a cold cathode field emission display. 14. The anode panel is formed between the phosphor layer and the substrate, and the display panel constitutes an anode panel of a cold cathode field emission display. Display panel. 15. The display panel according to claim 12, wherein the reflective film is made of aluminum or chromium.